Aminomethyl glutaronitriles

ABSTRACT

1. A PRODUCT OF THE FOLLOWING FORMULA:   AR-N(-R)-CH2-CH(-CN)-CH2-CH2-CN   WHEREIN AR IS NAPHTHYL OR A PHENYL RADICAL OF THE FORMULA:   R1,R2-PHENYL   WHREIN R1 AND R2 ARE INDEPENDENTLY HYDROGEN, ALKYL OF 1 TO 7 CARBONS, ALKOXY OF 1 TO 7 CARBONS, HALOGEN, OR ACETAMIDO, PROVIDING THAT THE POSITION OF THE RING PARA TO THE AMINO GROUP IS DEVOID OF SUBSTITUENTS; AND R IS HYDROGEN, AN ALKYL RADICAL OF 1-20 CARBON ATOMS OR A HALOALKYL OR DIHALOALKYL RADICAL OF 1-4 CARBON ATOMS.

United States Patent Office 3,839,400 Patented Oct. 1, 1974 ABSTRACT OFTHE DISCLOSURE There are disclosed dyestuff intermediates particularlyuseful for the production of disperse and soluble dyes for syntheticfibers by coupling with diazos, which intermediates have the followingformula:

Ar-N ON CH: C

CHgCHg C N wherein Ar is an aryl radical devoid of substituents in theposition para to the amino group and thus being capable of coupling atthe position para to the amine substituent, and -R is hydrogen, an alkylradical or a substituted alkyl radical. When the R substituent containsan amino radical there are also provided the quaternary ammonium saltsof these compounds which form water-soluble dyestuffs, and thecorresponding cyclic amides and imides.

BACKGROUND OF THE INVENTION Field of the Invention This inventionrelates to a novel class of dyestuff intermediates and more particularlyto dyestutf intermediates derived from alpha-methyleneglutaronitrilewhich are particularly useful for the production of disperse dyes forsynthetic fibers.

Description of the Prior Art With the introduction of synthetic fibersand synthetic textile materials, the demand for improved dyeingprocesses and products for use in dyeing these materials hassubstantially increased. The dyestuffs conventionally known to the artfor dyeing natural products were generally found unsatisfactory becauseof lack of fastness to light or for other reasons. Efforts to overcomethese drawbacks of conventional dyeing materials have resulted in thedevelopment of a large number of various types of dyestuffs which havebeen used in the dyeing of synthetic fibers.

A large body of art is concerned with azo dyestuffs and, particularlyfor azo dyestuffs useful in dyeing synthetic ztibers. The presentinvention provides a novel class of dyestuff intermediates which areeasily converted to disperse dyes which have been found particularlyuseful for dyeing synthetic fibers. These dyestutf intermediates arederived from alpha-methylene-glutaronitrile by reaction of this compoundwith an aryl amine. It has been found that these products areparticularly useful as dyestuff intermediates for coupling with a diazomoiety to form disperse dyes which are very eifective in coloringsynthetic fibers.

SUMMARY OF THE INVENTION It is accordingly one object of this inventionto provide a new class of dyestutf intermediates for use in theproduction of disperse dyes for synthetic fibers.

A further object of this invention is to provide a new class of dyestutfintermediates derived from the reaction of alpha-methyleneglutaronitrilewith an aryl amine.

A still further object of the invention is to provide a method for theproduction of the novel dyestulf intermediates of this invention.

Other objects and advantages of the present invention will becomeapparent as the description thereof proceeds.

In satisfaction of the foregoing objects and advantages, there isprovided by this invention a novel class of dyestutf intermediates ofthe following formula:

CH: C

CH CH: C N

wherein Ar is an aryl radical which is capable of coupling in paraposition to the amine substituent and R is hydrogen, an alkyl radical orsubstituted alkyl radical, all as defined more specifically hereinafter.When R is amino substituted there are also provided the quaternaryammonium derivatives which form water soluble dyes, as well as thecorresponding cyclic amides and imides. Also provided is a novel methodfor the production of these compounds by reaction ofalpha-methyleneglutaronitrile with an aryl amine.

DESCRIPTION OF PREFERRED EMBODIMENTS The novel dyestuff' intermediatesof the present invention react with diazos to provide dyes which areparticularly useful as disperse dyes for synthetic fibers andparticularly synthetic fibers such as the acetates, triacetates, nylons,polyesters and soluble basic dyes for polyacrylonitriles. When appliedto synthetic fibers, these dyestuif intermediates have been found tohave excellent fastness to light and sublimation. When a dyestuff isapplied by the thermosol method of dyeing, wherein the fiber treatedwith dyestuif is exposed to intense heat for a short time, and thedyestuif sublimes, the dyeing is affected in strength and brightness andthe equipment in surrounding areas becomes contaminated with dye. Theintermediates of the present invention provide products which overcomethese disadvantages of the prior art products and provide superior lightfastness, sublimation fastness, wash and perspiration fastness oversimilar dyes known in the art.

As indicated, the present invention is concerned with a novel class ofdyestutf intermediates which have been found particularly useful in theproduction of disperse dyes for synthetic fibers. These dyestuifintermediates are of the following formula:

wherein the above formula R and R are hydrogen, alkyl of l to 7 carbons,alkoxy of 1 to 7 carbons, halogen, trifiuoromethyl, an amide group i.e.,R CONH--, alkoxycarbonyl, i.e., R OCO where R is alkyl of 1 to 7 carbonsor phenyl and the like. Preferred substituents for R and R are hydrogen,methyl, methoxy, ethoxy, chloro,

bromo, fiuoro, CF acetamido benzamido and carbalkoxy. Highly preferredcompounds of this type are those of the formula:

N ON

CH2 CH CHzCHz CN wherein R is H, Cl, CH or R CONH--, R is H, CH loweralkoxy of l to 4 carbon atoms, and R and R are as described above.

The substituent R in the formula above is defined as hydrogen, an alkylradical or a substituted alkyl radical. More particularly, it ispreferred that R be hydrogen, an alkyl radical of 1-20 carbon atoms, ahaloalkyl or dihaloalkyl radical of 1-4 carbon atoms, cyanoalkyl wherethe alkyl group has 1-3 carbon atoms, aminoalkyl or diaminoalkyl of l4carbons, the quaternary ammonium, amide and imide derivatives thereof,hydroxyalkyl or dihydroxyalkyl of 14 carbon atoms, epoxyalkyl or 14carbon atoms, halohydroxyalkyl of 14 carbon atoms, sulfatoalkyl of l-4carbon atoms, cyanohydroxyalkyl of 1-4 carbon atoms, alkoxyalkyl oflcarbon atoms, carboalkoxyalkyl of l-lO carbon atoms, carboxyalkylesters of 1-10 carbon atoms or carboxyalkyl amides of 1-10 carbon atoms.Highly preferred substituents for R are as follows:

methyl ethyl propyl isopropyl butyl isobutyl tert-butyl amyl hexyl octyldodecyl octadecyl 2-chloroethyl 2-chloropropyl 3-ch1oropropyl4-chlorobutyl 2-bromoethyl 2,3-dichloropropy1 2-aminoethyltrimethylammoniumethyl pyridinium ethyl succirnidoethyl 2-cyanoethyl2-hydroxyethyl 2-hydroxypropyl S-hydroxypropyl 2,3-dihydroxypropyl2,3-epoxypropyl 3-chloro-2-hydroxypropyl 3-bromo-2-hydroxypropylZ-sulfatoethyl 3-cyano-2-hydroxypropyl 2-lower alkoxyethyl 3-loweralkoxypropyl 2-carbomethoxyethyl Z-carboethoxyethyl Z-carbobutoxyethyl3-carbomethoxypropyl carboxymethyl, methyl ester carboxymethyl, ethylester 1 carboxymethyl, butyl ester 2-carboxyethyl, ethyl estercarboxymethyl, dimethylamide The products of this invention are producedby the reaction of alpha-methyleneglutaronitrile of the formula:

CIIg=C CHzCHaCN with at least an equivalent amount of an aryl amine ofthe following formula:

wherein Ar and R have the values ascribed above. Preferred arylaminesfor use in the reaction are as follows:

The alpha-methyleneglutaronitrile and aryl amine may be generallyreacted in equivalent amounts, that is, on a mole to mole basis toobtain the products. The reaction is preferably carried out bycontacting the reactants in the presence of a small amount of a metalsalt catalyst and heating at a temperature of about 75 C. to the refluxpoint of the reaction for from 10 hours to 5 days. A solvent inert tothe reactants may be used in the reaction, for example, from about 0.5to about 5 moles of an inert solvent such as dioxane, methylpyrrolidone, dimethylformamide, alkyl ethers, carbon tetrachloride,aromatic hydrocarbons including benzene, toluene and xylene, halogenatedhydrocarbons such as chlorobenzene and the like may be used. It ishighly preferred however to use as the solvent an excess of up to 5moles of the amine reactant per mole of thealpha-methyleneglutaronitrile as excellent results are obtained thereby.As pointed out, the presence of catalytic amounts of any of the usualcondensation catalysts also favorably influence the reaction. Preferredcataylsts which may be used include cupric acetate, cuprous chloride,acetic acid and the like, all of which are well known in the art.

In practicing the reaction, the aryl amine, solvent or excess amine,catalyst and alpha-methyleneglutaronitrile are combined in theappropriate amounts and the reaction mixture heated to reflux until thereaction is complete. The reaction may also be carried out in anautoclave under pressure wherein the time required for the reaction willbe correspondingly reduced.

After completion of the reaction it is preferred to distill off theexcess amine or solvent although in some cases this may not benecessary. The product is then isolated in the usual manor of isolatingsolid products of this general type. One effective method is to drownthe reprocess, in practice it has been found preferable to initiallyreact the alpha-methyleneglutaronitrile with approximately an equivalentamount of a primary amine of the formula:

where Ar is as described above, rather than the secondary amine, as itis difiicult to react alpha-methyleneglutaronitrile with the abovedescribed secondary amines because of steric hindrance. In thisprocedure then, the reaction described is conducted and then the Rsubstituent is attached to the nitrogen of the amine. It has been foundthat the thus formed secondary amine can be alkylated to provide the Rsubstitutent in known manner.

If the reaction is conducted under such conditions that alkylation isrequired, that is, with the primary amine, alkylation may then becarried out for example by charging the required molar amount of theamine into an excess of an inert solvent such as aliphatic alcohol oraqueous alcohol solution and an equivalent amount, preferably an excess,of the sulfate of the group to be introduced. C-atalysts and othermaterials may be added as desired and known in the art. The reactionmixture is then heated, preferably at the reflux point of the system.Any solids are then filtered off, the solvent is removed by distillationand the solution cooled to provide the solid or semisolid product. Incases where a halogenated substituent or halo-substituted group isdesired, heating the hydroxyethyl product with an excess of ahalogenating agent, e.g., thionyl chloride, until hydrogen halideevolution ceases will produce products of this type.

In these products where R is a halogenated radical, such as a haloalkylradical, it is also preferred and within the scope of this inventionthat such compounds be further reacted with a tertiary amine to formpreferably tertiary or quaternary ammonium derivatives thereof. Thesequaternary ammonium salts form a valuable embodiment of the inventionsince they form dyestuffs which are water-soluble and thereforeexcellent basic dyes for polyacrylonitrile fibers.

To accomplish this, the N-haloalkylarylamine, prior to distilling offthe solvent, is treated with a tertiary amine. The reaction is warmedusually to or near the reflux and held there for 30 minutes to about 24hours. The intermediate can be isolated by evaporating to dryness. However, it is preferable to use it as a coupler without isolation to formthe dyestuffs. In this reaction, the tertiary amine may be of thefollowing formula:

wherein R is alkyl of 1 to 5 carbons, aralkyl of 7 to 14 carbon atoms ortogether with the nitrogen atom, a heterocyclic radical. Preferableamines for use in the reaction are as follows:

trimethylamine triethylamine tributylamine pyridine, picoline, lutidinesand other substituted pyridines morpholine quinoline These quaternaryammonium derivatives may be described by the following general formula:

9 R g-N034) 3X .Ar-N CN C nC CHgCHi C N wherein Ar is as defined above,R is a straight or branch chained alkylene group of 1 to 7 carbon atoms,R, is as above and X is the cation of a mineral acid, such as H01, HNO Hetc. In this formula R is preferably --CH cn cn -CH CH CH and X is C1 orBr Highly referred compounds within this group are those wherein R is asindicated and R is Various other subsequent reactions may be carried outon the products of the invention to provide a wide variety of newcompounds. For example, when the R substituent is a primary alkylhalide, Delepines reaction with hexamethylene tetramine may be carriedout to form the hexaminium halide which may then be hydrolyzed to theamine with aqueous mineral acid.

With respect to subsequent reactions carried out on the intermediates ofthe invention, there are also provided herein certain dye intermediatescontaining cyclic amides and imides. The dyes from these intermediatesform particularly color-fast dyes for hydrophobic fibers. Thesecompounds are prepared from the intermediates of this invention when Ris an amino substituted group, preferably such as aminoethyl asdescribed above. These novel intermediates may be described by thefollowing general formula:

wherein the Rs are independently selected from hydrogen, halogen,hydroxy, alkyl, substituted alkyl (e.g. chloroalkyl, bromoalkyl,hydroxyalkyl, al-koxyalkyl, cyanoalkyl, carbalkoxyalkyl, and the like),aryl, substituted aryl (e.g. phenyl, tolyl, xylyl, alkoxyphenyl,chlorophenyl, carbalkoxyphenyl, sulfamidophenyl, carboxamidophenyl,alkylsulfonylphenyl, alkylaminophenyl, and the like), cycloalkyl and thelike, wherein the alkyl groups have 1 to about 7 carbon atoms, the arylgroups have 6 to about 12 carbon atoms and the cycloalkyl groups have 3to about 8 carbon atoms;

A is selected from oxygen, nitrogen or sulfur;

n and p are integers having values from 0 to 15;

11+ p has a value of at least 2;

z is an integer having a value of 0 or 1;

r is an integer having a value of 0 or 1;

n+p+z+r have a value of at least 3;

m and q are the number of double bonds in the C and C moieties;

in the case where r is 1, z is 0, and n and p are each 1,

one R of each carbon atom may jointly form a 6- membered aryl ringhaving 6 to 12 carbon atoms.

I ON wherein r is as defined above. The radical represents the nucleusof a cyclic amide or imide preferably a five or six membered cyclicamide 0r imide, and L represents an organic radical containing from O to1 hetero atoms selected from oxygen, sulfur and nitrogen and beingselected from substituted or unsubstituted, saturated and unsaturatedradicals. The radical L can be substituted by the groups represented byR in Formula I above and may contain unsaturation as represented by mand q in Formula I.

Additionally, the above dyes can be in the form of their quaternarysalt.

These coupling components may be prepared in any conventional andconvenient manner. However, it has been found that a convenient methodof preparing the lactam compounds is by autoclaving the appropriateamine with an approximately equivalent amount of the desired lactone.The temperature, pressure and time of the autoclaving can varyconsiderably, a temperature of about ZOO-400 C., a pressure of about150-400 lbs., and a time from about to hours being preferred.

Specific lactones which may be used as reactants for producing thelactam substituent include the following:

butyrolactone and the following substituted butyrolactones:

3-methyl 4-methyl S-methyl 3-ethyl 4-ethyl S-ethyl 3,3-dimethyl4,4-dimethyl 5,5-dimethyl valerolactone and the following substitutedvalerolactones:

3-methyl 4-rnethy1 S-methyl 6-methyl 'y-valerolactone-ch1oro-y-methylbutyrolactone 'y-chloromethylbutyrolactonea-bromo-y-chloromethylbutyrolactone 6-caprolactone -r-caprolactone3-ethylbutyrolactone 5,S-dimethylbutyrolactone 4,5-dimethylbutyrolactone4,bromo-3,B-dimethylbutyrolactone 5-ethyl-5-methylbutyrolactone3,3,4-trimethylbutyrolactone S-amylbutyrolacetone While the aboverepresents a rather broad class of compounds of this type, a highlypreferred class comprises compounds of the formula:

0 ll /C s 2) 5 Ar-N CHzCH CH2 C HzC N wherein Ar and R are as above, Ris 1:0 or H r is 0 or 1, and a is an integer of 1 to 12, together withcondensed aryl rings attached to adjacent carbon atoms of the ring.Preferred compounds of this class are those wherein the amide moiety isof the formulae:

In preparing these compounds, the amides are prepared from thecorresponding lactones as described above. However, in preparing theimides, a preferred procedure is to react the amine with a dibasic acidanhydride including the anhydrides of malonic acid, succinic acid,glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid,sebacic acid and brassylic acid as well as the lower alkyl substitutedderivatives thereof and these anhydrides which have benzene ringsattached to adjacent carbon atoms on the ring, e.g. phthalic anhydride.

This reaction is conducted by contacting the amine and anhydride inmolar ratios and heating gradually until an exothermic reaction isinitiated. After the temperature begins to fall, it is then heated at atemperature of C. for 1 to 2 hours, cooled below 100 C. and drowned intoan excess of ice Water containing a base. The product is then filteredoff and dried.

The products resulting from this reaction are imide r derivatives of theformula:

wherein Ar, R and a are as defined above, together with these compoundswhich have benzene rings condensed at adjacent carbon atoms on the imidering.

As pointed out above, the products of this invention are very unique inthat they provide a novel class of dyestulf intermediates particularlyfor use in the production-- of both dispersed and water-soluble dyes andwater-soluble cationic dyes for synthetic fibers. This is possiblebecause the position para to the nitrogen group on the aryl ring is freeof substituents so that the intermediates can be coupled with a diazocompound to form the dye. Thus in one embodiment, the intermediates arecoupled to a diazo of the formula:

e NEN x wherein X is a negative group, such as N0 lower alkyl sulfonyl,CN, CF lower carboalkoxy, sulfonarnide, monoor di-lower alkylsulfonamide, carboxamide, and monoor di-lower alkyl sulfonamide,carbonyland sulfonyl-morpholide and piperidide; Y is H, Cl, Br, F or thesame as X; Z is H, Cl, Br or F, CN, CF lower carboalkoxy; and X is thecation of a mineral acid, e.g. C1 or Br Diazotized p-nitroaniline,2,4-dinitro-6-chloroaniline, 2,6-dichloro-4-nitroaniline and2-chloro-4-nitroaniline are especially preferred reactants.

The diazotization of the amine and coupling reaution may be carried outin a known manner, for example, as'

shown in US. Pat. Nos. 2,099,525 or 3,079,377, by reacting the aminewith nitrosyl sulfuric acid at a temperature,

of about -30 C. or sodium nitrite in aqueous mineral acid such assulfuric acid or hydrochloric acid at a temperature of about 020 C. Theexcess nitrite may be later removed by treatment with sulfamic acid. Theresulting diazotized amine is then coupled with an equivalent amount orup to equivalent excess of by Weight of the intermediate coupler of thisinvention by adding a solution of the latter in dilute mineral acidaqueous solution to the diazo solution portionwise over a period of timeif necessary to complete the coupling. The resulting mixture issubsequently brought up to a pH of 4-5 by the careful addition of sodiumacetate or a base such as an alkali metal hydroxide, alkali metalcarbonate or alkali metal bicarbonate, with agitation and the solidproduct separated if desired.

If coupler amine is basic enough, it can be dissolved in dilute aqueousmineral acid (e.g. HCl or H 50 containing a small amount of sulfamicacid (which destroys any excess nitrous acid) and the diazo run into thecoupler solution in an alternative coupling reaction.

The dye is usually recovered as a powder and can be treated withdispersing agents in the same manner employed in the preparation ofdispersed acetate dye pastes to obtain a dispersible dye. Alternatively,a 40-50 percent active dispersed powder can be employed in a similarmanner but in lesser amounts. On the other hand, when water-soluble dyesare formed from the quaternary ammonium intermediates they may be usedas solutions in dyeing polyacrylonitriles particularly.

Dispersing agents such as sodium lignosulfonate and alkylarylsulphonatesand the products resulting from the condensation of sulphonated aromaticderivtives with alde hydes, such as the methylene-dinaphthylsulphonates,are particularly valuable auxiliary substances since they allow thepreparation of good dispersion of the dyestuffs and facilitate thetaking up of the latter on the fibers. On the other hand, carriers, suchas monoor poly-chlorinated derivatives of the benzene series ordiphenyl, can be added to the dye bath or to the printing pastes. Thesesubstances exert a swelling action of the fibers and are capable ofimproving the tinctorial yield.

In carrying out the dyeing procedure of the persent invention, about 20weight percent active dispersed paste of the dyestufl is dissolved inWater at concentrations of from about 1.0 to 15.0 ounces per gallon. Thesolution is thickened to suitable padding consistency by the addition ofconventional thickeners such as gum tragacanth in quantities normallyabout twice that of the water employed.

The dyeing may be carried out by any desired method such as thethermosol method of high temperature dyeing. Thus dyeing may be effectedby impregnating the synthetic fibers by padding or printing with anaqueous suspension or solution of the dye at an elevated temperature,drying the fiber and subsequently subjecting to a heat treatment at atemperature of from about 390 F. to about 440 F. for a period of timesufficient to develop the full color.

The following examples illustrate the invention but are not intended tobe limitative thereto. In the examples and throughout the specification,parts are by weight unless otherwise indicated.

EXAMPLE 1 A total of 321 grams of m-toluidine, 106 grams of 0!.-methyleneglutaronitrile and 10 grams of cupric acetate are combined andheated to and maintained at a temperature of 125130 C. and 60 hours.Excess m-toluidine is distilled off, the brown syrupy reaction mass iscooled to about 90 C. and gradually run into a mixture of 2000 cc. ofwater and 1000 grams of ice with vigorous stirring and in an ice bath.The crystals are filtered, washed several times with cold water anddried. An 82% yield, based on the ot-methyleneglutaronitrile, isobtained.

The product is believed to have the formula:

@ CH: C H

CHBCHZ C N Recrystallization from isopropanol gives light browncrystals. Carbon analysis showed 073.80%.

EXAMPLE 2 A total of 100 cc. of dioxane, 3.7 grams of cupric acetate,108 grams of N-ethyl-m-toluidine and grams of t-methyleneglutaronitrileare combined and heated to about C. for 44 hours. An additional 3.7grams of cuprous chloride and 55 cc. glacial acetic acid are added andheating, is continued for another 42 hours. The charge 1s cooled to 0-5C., filtered, washed with cold water and dried. The product has theformula:

CHgCHz C When spot tested with p-nitroaniline diazo, an orange colordevelops, with 2,4-dinitro-6-chloroaniline diazo a vlolet colordevelops, and with 2-chloro-4-nitrodiaz0 a reddlsh bordeaux colordevelops.

EXAMPLE 3 grams of m-aminoacetam'lide, 212 grams ofa-methyleneglutaronitrile and 10 grams of cupric acetate are combinedand heated to the reflux and held there for 60 hours. Excessa-methyleneglutaronitrile is distilled off. The reaction mass is cooledsomewhat and then drowned in a mixture of 2000 cc. of water and 1000gms. of ice with vigorous stirring and in an ice bath. The crystals arefiltered, washed with cold water and dried. The product has the formula:

Q4 ON I 011261 NH O O CH:

EXAMPLE 4 CHzCHzCN EXAMPLE 5 311 grams of N-(2-chloroethyl)aniline, 106grams of a-methyleneglutaronitrile and 10 grams of cupric acetate arecombined, and heated to and maintained at the reflux for 60 hours. Theexcess N-(2-chloroethyl)aniline is distllled off, the reaction mass iscooled somewhat and then drowned into a mixture of 2000 cc. of water and1000 gms. of ice with rapid stirring in an ice bath. The crystals areCHzCHzCN 130 grams of this product are then refluxed with 500 cc. of 40%aqueous trimethylamine solution until a small sample removed is found tobe completely water soluble, a sign of complete conversion to thequaternary ammonium salt. The product has the formula:

CzHiCl CHQCHZGN EXAMPLE 6 21.3 grams of the product of Example 1 (0.1mol), 16 grams of ethylene chlorohydrin, 20 grams of precipitated chalk,150 cc., isopropanol, and 50 cc. of water are refluxed for 24 hours. Thedissolved calcium is precipitated as CaSO the resulting reaction massfiltered from the CaSO the isopropanol distilled off from the filtrate,the aqueous solution cooled in an ice bath and the product filtered offand dried in a 50 C. vacuum oven.

The resulting N-hydroxyethyl-N-dicyanobutyl compound is then refiuxedwith excess thionyl chloride until no further evolution of HCl occursand the excess thionyl chloride is distilled off to provide theN-chloroethyl-N- dicyanobutyl derivative.

The resulting N-chloroethyl-N-dicyanobutyl compound is reacted accordingto Delepines method by heating with hexamethylene tetramine to form thehexaminimum chloride and the hydrolyzed by heating with ethanol andconcentrated HCl to the HCl salt of the N-aminoethyl-N- dicyanobutylderivative. The amine is set free by neutralizing with sodium carbonate,filtered oflf cold and allowed to air dry. 27.6 grams (0.1 mol) of theaminoethyl compound and grams (0.1 mol) of succinic anhydride are mixedintimately and heated gradually until an exothermic reaction begins.After the temperature begins to fall, it is heated to l35-l40 C. for onehour. The melt is then cooled below 100 C. and drowned into 2 liters ofice and water containing 10 grams of Na CO The product is filteredoff-and washed with water and dried. It has the following structure:

(IJN CH; C HCHQCHI C N CHgCHzN C 0 CH2 EXAMPLE 7 44.5 grams of thecoupler of Example 1 are dissolved in a mixture of 325 cc. ofconcentrated hydrochloric acid and 175 cc. of water and clarified fromslight insolubles. 29 grams of p-nitroaniline are diazotized in knownmanner and run into the above prepared coupler solution which is at atemperature of 010 C. Water is added to a total volume of 3000 cc. Afterseveral hours stirring, the orange dye is filtered, washed with coldwater and dried.

8 grams of dye are dispersed by viscous milling with 11 grams MarasperseCB (sodium lignosulfonate), 0.5 grams of Nekal BX78 (sodiumalkylnaphthalenesulfonate), 0.5 grams of Nekal WS-25 and 0.2 gramssodium carbonate. Dacron is colored in bright solid orange shade,especially fast to sublimation at the high temperatures used in thethermosol dyeing process, and having good light fastness.

The invention has been described herein with reference to certainpreferred embodiments. However, as obvious variations will appear tothose skilled in the art, it is not to be considered as limited thereto.

What is claimed is:

1. A product of the following formula:

Ar-N ON CHzCH CI-IzCI-I CN wherein Ar is naphthyl or a phenyl radical ofthe formula:

wherein R and R are independently hydrogen, alkyl 0f 1 to 7 carbons,alkoxy of 1 to 7 carbons, halogen, or acetamido, providing that theposition on the ring para to the amino group is devoid of substituents;and R is hydrogen, an alkyl radical of l-20 carbon atoms or a haloalkylor dihaloalkyl radical of 1-4 carbon atoms.

2. A product according to claim 1 wherein Ar is a radical of theformula:

where R is H, Cl, CH and acetamido or R is H, CH or alkoxy of 1-4 carbonatoms.

3. A product according to claim 2 wherein R is methyl and R and R arehydrogen.

4. A product according to claim 2 wherein R is methyl, R is hydrogen andR is ethyl.

5. A product according to claim 2 wherein R is acetamido and R and R arehydrogen.

6. A product according to claim 2 wherein R is methyl, R is methoxy andR is hydrogen.

7. A product according to claim 2 wherein R and R are H and R is2-chloroethyl.

OTHER REFERENCES Ichikawa et al.: Chemical Abstracts, v01. 74, p. 270(1971).

ELBERT L. ROBERTS, Primary Examiner D. H. TORRENCE, Assistant ExaminerUS. Cl. X.R.

260-144, 152, 205, 247.2 A, 247.2 B, 247.5 R, 281, 293.75, 294.9, 283CN, 348 A, 348 R, 465 D

1. A PRODUCT OF THE FOLLOWING FORMULA: